Bleaching composition

ABSTRACT

A bleaching composition comprises a peroxide and an amphoteric organic per acid precursor. In particular the amphoteric organic per acid precursor is a quaternary ammonium salt has the following formula in which Z is sulfonate or carboxylate and is a new compound. ##STR1##

The invention relates to a bleaching composition and a novel amphotericcompound to serve as an activator for the composition.

STATEMENT OF THE PRIOR ARTS

Since chlorine-containing bleaching agents have the defects that thetextiles to which they are applicable are limited, that they cannot beused for bleaching colored or figured cloths and that they have apeculiar smell, the use of oxygen-containing bleaching agents free ofthese defects has generally spread recently.

Among the oxygen-containing bleaching agents, sodium percarbonate andsodium perborate are particularly useful in virtue of their bleachingcapacity and stability.

The oxygen-containing bleaching agents are used in combination withvarious bleaching activators, since their bleaching power is weaker thanthat of the chlorine-containing ones. Investigations have been made onvarious bleaching activators including, for examples, nitriles such asacetonitrile, malononitrile, phthalonitrile andbenzoyliminodiacetonitrile; O-acetylated compounds such as glucosepentaacetate, octaacetylsucrose, triacetin, sorbitol hexaacetate,acetoxybenzenesulfonates, triacetylcyanuric acid and methylchloroformate; N-acylated compounds such asN,N,N',N'-tetraacetylethylenediamine and tetraacetylglycolyluril,N-benzoylimidazole, di-N-acetyldimethylglyoxime,1-phenyl-3-acetylhydantoin, N,N-diacetylaniline, N-acetyldiglycolimideand diacetylmethylenediformamide; acid anhydrides such as phthalic,succinic, benzoic, glutaric, alkylsulfuric and carboxylic/organicsulfonic acid anhydrides; sulfonyl oximes such asdi(methanesulfonyl)dimethylglyoxime; acylated phosphoric acid salts suchas diethylbenzoylphosphoric acid salts; phenyl sulfonate esters; organicphosphoric azides such as diphenylphosphinic azides; disulfones such asdiphenyl disulfone; and other compounds such as N-sulfonylimidazole,cyanamide, halogenated triazines andN,N-dimethyl-N-octyl-N-10-carbophenoxydodecylammonium chloride. However,no sufficient bleaching power could be obtained even when such anactivator was used in combination with the oxygen-containing bleachingagent.

SUMMARY OF THE INVENTION

After intensive investigations made for the purpose of developing anoxygen-containing bleaching agent having a higher bleaching power, theinventors have found that the object can be attained by using acombination of a peroxide and an amphoteric organic per acid precursor.The present invention has been completed on the basis of this finding.

A bleaching composition of the invention comprises a peroxide and anamphoteric organic per acid precursor, preferably at a molar ratio of99.9/0.1 to 20/80.

The organic per acid precursor is preferred to be an amphoteric compoundhaving the formula (I): ##STR2## wherein: X represents a group of theformula: ##STR3## in which R₁ and R₂ each represents a substituted orunsubstituted, straight-chain or branched alkyl or alkenyl group having1 to 30 carbon atoms, an alkaryl group (in which the alkyl group has 1to 24 carbon atoms) or the two R groups may form a heterocyclic ringhaving 4 to 6 carbon atoms, together with N, S or P, R₃ represents asubstituted or unsubstituted, straight-chain or branched alkyl oralkenyl group having 1 to 30 carbon atoms, an alkaryl group (in whichthe alkyl group has 1 to 16 carbon atoms) or a heterocyclic ring having4 to 6 carbon atoms together with the two R groups bonded to N, S or Por --(C₂ H₄ O)_(x) H (in which x is a number of 1 to 20), Y represents astraight-chain or branched alkylene group having 1 to 20 carbon atoms,and Z represents an SO₃ ⁻ or CO₂ ⁻ group.

It is more preferable that in the formula (I) X is --N⁺ R₁ R₂ R₃, R₁ isan alkyl having 1 to 22 carbon atoms or a hydroxyalkyl having 1 to 22carbon atoms and R2 and R3 each are an alkyl having 1 to 3 carbon atoms,Y is an alkylene having 1 to 5 carbon atoms and Z is sulfonate orcarboxylate.

The composition of the invention may further contain a conventionaldetergent component.

The invention provides an amphoteric compound having the formula (V):##STR4## in which R1 is an alkyl group having 1 to 22 carbon atoms, R2and R3 each are a lower alkyl, n is an integer of 1 to 5, Z is --COO⁻,--COOM, --SO₃ ⁻ or --SO₃ M and M is a cation.

The compound having the formula (V) in which R₁ is an alkyl having 1 to16 carbon atoms and R₂ and R₃ each are an alkyl having 1 to 3 carbonatoms preferably provides the bleaching effect. In particular thecompound having methyl for R₁ is useful from the practical point ofview. In addition, the compound in which R₁ is an alkyl having 8 to 16carbon atoms does not only provide the bleaching effect, but also thesurface activity.

The compound having the formula (I) in which Z is --SO₃ ⁻ can beobtained, for example, by the following process:

a tertiary amine is reacted with a halocarboxylic acid in a solvent suchas an alcohol or acetone at room temperature or under reflux of thesolvent to obtain a quarternary amine (II): ##STR5## wherein R₁, R₂, R₃and R₄ each represents an alkyl group, n represents an integer of 1 to 5and X represents a halogen atom.

Then, the compound (II) is hydrolyzed in the presence of an alkalinecatalyst such as KOH or NaOH in a solvent mixture such as a mixture ofwater with an alcohol to obtain an amphoteric compound (III): ##STR6##

The compound (III) is reacted with thionyl chloride in dichloromethaneor ethanol-free chloroform, i.e., in a solvent free from any compoundreactive with an acyl chloride, such as water or an alcohol, to obtainan acyl chloride (IV): ##STR7##

The obtained chloride (IV) is reacted with disodium p-phenolsulfonate ina solvent in which the compound (IV) is soluble or homogeneouslydispersible, such as dimethoxyethane (DME), under reflux of the solventto obtain an intended amphoteric compound (I): ##STR8##

The compound having the formula (I) in which Z is --CO₂ ⁻ can beobtained, for example, by the following process: ##STR9## wherein R₁,R₂, R₃ and R₄ stand for each an alkyl group, n is an integer of from 1to 5 and X stands for a halogen atom.

Then, the compound (II) is hydrolyzed with an alkali catalyst such asKOH or NaOH in a mixed solvent such as water/alcohol to obtain anamphoteric compound represented by the formula (III), as indicatedbelow: ##STR10##

The compound (III) is reacted with thionyl chloride in the presence of asolvent not containing a substance capable of reacting with an acidchloride, such as water or an alcohol, for example, in dichloromethaneor chloroform subjected to an ethanol-removing treatment, to obtain anacid chloride of the formula (IV), as indicated below: ##STR11##

Then, the acid chloride (IV) is reacted with p-hydroxybenzoic acid(typical instance) in tetrahydrofuran (THF) as the solvent to obtain theintended amphoteric compound (I).

The amphoteric organic per acid precursor remarkably improves thebleaching power of the peroxide.

The peroxide in the present invention is preferably hydrogen peroxide ora peroxide capable of generating hydrogen peroxide in its aqueoussolution.

The peroxides capable of generating hydrogen peroxide in an aqueoussolution thereof include organic and inorganic hydrogen peroxide adductssuch as sodium carbonate/hydrogen peroxide adduct, sodiumtripolyphosphate/hydrogen peroxide adduct, sodium pyrophosphate/hydrogenperoxide adduct, urea/hydrogen peroxide adduct and 4Na₂ SO₄.2H₂ O₂.NaCl.They further include inorganic peroxides such as sodium perboratemonohydrate, sodium perborate tetrahydrate, sodium peroxide and calciumperoxide. Among them, sodium carbonate/hydrogen peroxide adduct, sodiumperborate monohydrate and sodium perborate tetrahydrate are particularlypreferred.

The molar ratio of the peroxide to the organic per acid precursor usedin the present invention is 99.9/0.1 to 20/80.

The bleaching composition of the present invention may contain knownadditives usually contained in bleaching compositions in addition to theabove-mentioned indispensable components. For example, the compositionmay contain a builder such as a water-soluble inorganic builder, e.g.,sulfate, carbonate, bicarbonate, silicate or phosphate or an organicbuilder, e.g., ethylenediaminetetraacetate, tartrate or citrate.Stabilizers for the peroxide or hydrogen peroxide adduct usable in thepresent invention include known magnesium salts such as magnesiumsulfate, magnesium silicate, magnesium chloride, magnesiumfluorosilicate, magnesium oxide and magnesium hydroxide, and silicatessuch as sodium silicate. If necessary, the bleaching composition mayfurther contain an antiredeposition agent such ascarboxymethylcellulose, polyvinylpyrrolidone or polyethylene glycol, aswell as surfactant, enzyme, fluorescent brightener, dye, pigment,flavor, etc.

The bleaching detergent composition of the invention may comprises thefollowing in addition to the above shown bleaching agents.

[1] SURFACTANTS

(1) Straight-chain or branched alkylbenzenesulfonate salts having analkyl group of 10-16 carbon atoms on the average.

(2) Alkyl or alkenyl ether sulfate salts having a straight-chain orbranched alkyl or alkenyl group of 10-20 carbon atoms on the average,0.5-8 mol on the average of ethylene oxide, propylene oxide or butyleneoxide in the molecule and an addition ratio of ethylene oxide/propyleneoxide of 0.1/9.9-9.9/0.1 or ethylene oxide/butylene oxide of0.1/9.9-9.9/0.1

(3) Alkyl or alkenyl sulfate salts having an alkyl or alkenyl group of10-20 carbon atoms on the average.

(4) Olefinsulfonate salts having 10-20 carbon atoms on the average inthe molecule.

(5) Alkanesulfonate salts having 10-20 carbon atoms on the average inthe molecule.

(6) Saturated or unsaturated fatty acid salts having 10-24 carbon atomson the average in the molecule.

(7) Alkyl or alkenyl ether carboxylate salts having an alkyl or alkenylgroup of 10-20 carbon atoms on the average, 0.5-8 mol on the average ofethylene oxide, propylene oxide or butylene oxide in the molecule and anaddition ratio of ethylene oxide/propylene oxide of 0.1/9.9-9.9/0.1 orethylene oxide/butylene oxide of 0.1/9.9 to 9.9/0.1.

(8) α-Sulfo fatty acid salts or esters of the general formula: ##STR12##wherein Y represents an alkyl group having 1-3 carbon atoms or acounter-ion, Z represents a counter-ion and R represents an alkyl oralkenyl group having 10-20 carbon atoms.

As the counter-ions of anionic surfactants, there may be mentioned, forexample, ions of alkali metals such as sodium and potassium, alkalineearth metals such as calcium and magnesium, ammonium, alkanolaminescontaining 1-3 alkanol groups having 2 or 3 carbon atoms such asmonoethanolamine, diethanolamine, triethanolamine andtriisopropanolamine.

(9) Amino acid-type surfactants of the general formulae: ##STR13##wherein R₁ represents an alkyl or alkenyl group having 8-24 carbonatoms, R₂ represents hydrogen or an alkyl group having 1-2 carbon atoms,R₃ represents an amino acid residue and X represents an alkali metal oralkaline earth metal ion. ##STR14## wherein R₁, R₂ and X have the samemeanings as above and n represents an integer of 1-5. ##STR15## whereinR₁ has the same meaning as above and m represents an integer of 1-8.##STR16## wherein R₁, R₃ and X have the same meaning as above and R₄represents hydrogen, or an alkyl or hydroxyalkyl group having 1-2 carbonatoms. ##STR17## wherein R₂, R₃ and X have the same meaning as above andR₅ represents a β-hydroxyalkyl or β-hydroxyalkenyl group having 6-28carbon atoms. ##STR18## wherein R₃, R₅ and X have the same meaning asabove.

(10) Phosphate ester surfactants: ##STR19## wherein R' represents analkyl or alkenyl group having 8-24 carbon atoms, n'+m' represents 3 andn' represents a number of 1-2. ##STR20## wherein R' has the same meaningas above, n"+m" represents a number of 3 and n" represents a number of1-3. ##STR21## wherein R', n" and m" have the same meaning as above andM represents Na, K or Ca.

(11) Sulfonic acid-type amphoteric surfactants of the general formulae:##STR22## wherein R₁₁ represents an alkyl or alkenyl group having 8-24carbon atoms, R₁₂ represents an alkylene group having 1-4 carbon atoms,R₁₃ represents an alkyl group having 1-5 carbon atoms, R₁₄ represents analkylene or hydroxyalkylene group having 1-4 carbon atoms. ##STR23##wherein R₁₁ and R₁₄ have the same meaning as above and R₁₅ and R₁₆ eachrepresent an alkyl or alkenyl group having 8-24 or 1-5 carbon atoms.##STR24## wherein R₁₁ and R₁₄ have the same meaning as above and n1represents an integer of 1-20.

(12) Betaine-type, amphoteric surfactants of the general formulae:##STR25## wherein R₂₁ represents an alkyl, alkenyl, β-hydroxyalkyl orβ-hydroxyalkenyl group having 8-24 carbon atoms, R₂₂ represents an alkylgroup having 1-4 carbon atoms and R₂₃ represents an alkylene orhydroxyalkylene group having 1-6 carbon atoms. ##STR26## wherein R₂₁ andR₂₃ have the same meaning as above and n2 represents an integer of 1-20.##STR27## wherein R₂₁ and R₂₃ have the same meaning as above and R₂₄represents a carboxyalkyl or hydroxyalkyl group having 2-5 carbon atoms.

(13) Polyoxyethylene alkyl or alkenyl ethers having an alkyl or alkenylgroup of 10-20 carbon atoms on the average and 1-30 mol of ethyleneoxide added.

(14) Polyoxyethylene alkylphenyl ethers having an alkyl group of 6-12carbon atoms on the average and 1-25 mol of ethylene oxide added.

(15) Polyoxypropylene alkyl or alkenyl ethers having an alkyl or alkenylgroup of 10-20 carbon atoms on the average and 1-20 mol of propyleneoxide added.

(16) Polyoxybutylene alkyl or alkenyl ethers having an alkyl or alkenylgroup of 10-20 carbon atoms on the average and 1-20 mol of butyleneoxide added.

(17) Nonionic surfactants having an alkyl or alkenyl group of 10-20carbon atoms on the average and 1-30 mol in total of ethylene oxide andpropylene oxide added or ethylene oxide and butylene oxide added (ratioof ethylene oxide to propylene oxide or butylene oxide being 0.1/9.9 to9.9/0.1).

(18) Higher fatty acids alkanolamides or alkylene oxide adducts thereofof the general formula: ##STR28## wherein R'₁₁ represents an alkyl oralkenyl group having 10-20 carbon atoms, R'₁₂ represents H or CH₃, n3represents an integer of 1-3 and m3 represents an integer of 0-3.

(19) Sucrose/fatty acid esters comprising fatty acids having 10-20carbon atoms on the average and sucrose.

(20) Fatty acid/glycerol monoesters comprising fatty acids having 10-20carbon atoms on the average and glycerol.

(21) Alkylamine oxides of the general formula: ##STR29## wherein R'₁₃represents an alkyl or alkenyl group having 10-20 carbon atoms and R'₁₄and R'₁₅ each represent an alkyl group having 1-3 carbon atoms.

(22) Cationic surfactants of the general formulae: ##STR30## wherein atleast one of R'₁, R'₂, R'₃ and R'₄ represents an alkyl or alkenyl grouphaving 8-24 carbon atoms and the remainder represents an alkyl grouphaving 1-5 carbon atoms and X' represents a halogen. ##STR31## whereinR'₁, R'₂, R'₃ and X' have the same meaning as above. ##STR32## whereinR'₁, R'₂ and X' have the same meaning as above, R'₅ represents analkylene group having 2-3 carbon atoms and n4 represents an integer of1-20.

The composition probably contains at least one of the above surfactantsin an amount of at least 10 wt. %.

As preferred surfactants, there may be mentioned above surfactants (1),(2), (3), (4), (5), (6), (11)-No. 2, (12)-No. 1, (13), (14), (15), (17)and (18).

[2] DIVALENT METAL ION SEQUESTERING AGENTS

The composition may contain 0-50 wt. % of one or more builder componentsselected from the group consisting of alkali metal salts or alkanolaminesalts of the following compounds:

(1) Salts of phosphoric acids such as orthophosphoric acid,pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid,hexametaphosphoric acid and phytic acid.

(2) Salts of phosphonic acids such as ethane-1,1-diphosphonic acid,ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acidand its derivatives, ethane-hydroxy-1,1,2-triphosphonic acid,ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonicacid.

(3) Salts of phosphono carboxylic acids such as2-phosphonobutane-1,2-dicarboxylic acids,1-phosphonobutane-2,3,4-tricarboxylic acids andα-methylphosphonosuccinic acid.

(4) Salts of amino acids such as aspartic acid, glutamic acid andglycine.

(5) Salts of aminopolyacetic acids such as nitrilotriacetic acid,iminodiacetic acid, ethylenediaminetetraacetic acid,diethylenetriaminepentaacetatic acid, glycol ether diaminetetraaceticacid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaaceticacid and dienkolic acid.

(6) High-molecular electrolytes such as polyacrylic acid, polyaconiticacid, polyitaconic acid, polycitraconic acid, polyfumaric acid,polymaleic acid, polymesaconic acid, poly-α-hydroxyacrylic acid,polyvinylphosphonic acid, sulfonated polymaleic acid, maleicanhydride/diisobutylene copolymer, maleic anhydride/styrene copolymer,maleic anhydride/methyl vinyl ether copolymer, maleic anhydride/ethylenecopolymer, maleic anhydride/ethylene cross-linked copolymer, maleicanhydride/vinyl acetate copolymer, maleic anhydride/acrylonitrilecopolymer, maleic anhydride/acrylate ester copolymer, maleicanhydride/butadiene copolymer, maleic anhydride/isoprene copolymer,poly-β-keto carboxylic acid derived from maleic anhydride and carbonmonoxide, itaconic acid/ethylene copolymer, itaconic acid/aconitic acidcopolymer, itaconic acid/maleic acid copolymer, itaconic acid/acrylicacid copolymer, malonic acid/methylene copolymer, mesaconic acid/fumaricacid copolymer, ethylene glycol/ethylene terephthalate copolymer,vinylpyrrolidone/vinyl acetate copolymer, 1-butene-2,3,4-tricarboxylicacid/itaconic acid/acrylic acid copolymer, quaternary ammoniumgroup-containing polyester polyaldehyde carboxylic acids, cis-isomer ofepoxysuccinic acid, poly[N,N-bis(carboxymethyl)acrylamide], poly(hydroxycarboxylic acid), starch succinate, starch maleate, starchterephthalate, starch phosphate ester, dicarboxystarch,dicarboxymethylstarch and cellulose succinate esters.

(7) Non-dissociating high-molecular compounds such as polyethyleneglycol, polyvinyl alcohol, polyvinylpyrrolidone and cold water-soluble,urethanated polyvinyl alcohol.

(8) Salts of dicarboxylic acids such as oxalic acid, malonic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid and decane-1,10-dicarboxylic acid; salts of diglycolicacid, thiodiglycolic acid, oxalacetic acid, hydroxydisuccinic acid,carboxymethylhydroxysuccinic acid and carboxymethyltartronic acid; saltsof hydroxy carboxylic acids such as glycolic acid, malic acid,hydroxypivalic acid, tartaric acid, citric acid, lactic acid, gluconicacid, mucic acid, glucuronic acid and dialdehydostarch oxide; salts ofitaconic acid, methylsuccinic acid, 3-methylglutaric acid,2,2-dimethylmalonic acid, maleic acid, fumaric acid, glutamic acid1,2,3-propanetricarboxylic acid, aconitic acid,3-butene-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid,ethanetetracarboxylic acid, ethenetetracarboxylic acid,n-alkenylaconitic acid, 1,2,3,4-cyclopentanetetracarboxylic acid,phthalic acid, trimesic acid, hemimellitic acid, pyromellitic acid,benzenehexacarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acidand tetrahydrofuran-2,2,5,5-tetracarboxylic acid; salts of sulfonatedcarboxylic acids such as sulfoitaconic acid, sulfotricarballylic acid,cysteic acid, sulfoacetic acid and sulfosuccinic acid; carboxymethylatedsucrose, lactose and raffinose, carboxymethylated pentaerythritol,carboxymethylated gluconic acid, condensates of polyhydric alcohols orsaccharides with maleic anhydride or succinic anhydride, condensates ofhydroxy carboxylic acids with maleic anhydride or succinic anhydride,and organic acid salts such as CMOS and Builder M.

(9) Aluminosilicates:

No. 1. Crystalline aluminosilicates of the formula:

    x'(M'.sub.2 O or M"O)·Al.sub.2 O.sub.3 ·y'(SiO.sub.2)·w'(H.sub.2 O)

wherein M' represents an alkali metal atom, M" represents an alkalineearth metal atom exchangeable with calcium, and x+, y' and w' representmole numbers of the respective components and generally, they are asfollows: 0.7≦x'≦1.5, 0.8≦y'≦6 and w' being a positive number.

No. 2. Detergent builders having the following general formula areparticularly preferred:

    Na.sub.2 O·Al.sub.2 O.sub.3 ·nSiO.sub.2 ·wH.sub.2 O

wherein n represents a number of 1.8-3.0 and w represents a number of1-6.

No. 3. Amorphous aluminosilicates of the formula:

    x(M.sub.2 O)·Al.sub.2 O.sub.3 ·y(SiO.sub.2)·w(H.sub.2 O)

wherein M represents sodium and/or potassium atom, and x, y and wrepresent mole numbers of the respective components within the followingranges:

    0.7≦x≦1.2

    1.6≦y≦2.8

w: any positive number including O.

No. 4. Amorphous aluminosilicates of the formula:

    X(M.sub.2 O)·Al.sub.2 O.sub.3 ·Y(SiO.sub.2)·Z(P.sub.2 O.sub.5)·ω(H.sub.2 O)

wherein M represents Na or K and X, Y, Z and ω represent mole numbers ofthe respective components within the following ranges:

    0.20≦X≦1.10

    0.20≦Y≦4.00

    0.001≦Z≦0.80

ω: any positive number including 0.

[3] ALKALIS OR INORGANIC ELECTROLYTES

The composition may contain also 1-50 wt. %, preferably 5-30 wt. %, ofone or more alkali metal salts selected from the following compounds asthe alkali or inorganic electrolyte: silicates, carbonates and sulfates.Further, the composition may contain organic alkalis such astriethanolamine, diethanolamine, monoethanolamine andtriisopropanolamine.

[4] ANTIREDEPOSITION AGENTS

The composition may contain 0.1-5% of one or more of the followingcompounds as antiredeposition agent(s): polyethylene glycol, polyvinylalcohol, polyvinylpyrrolidone and carboxymethylcellulose.

[5] ENZYMES (enzymes which exhibits the essential enzymatic effectsthereof in the deterging step)

As the enzymes, the following enzymes may be mentioned (classified withrespect to their enzymatic reactivities): Hydrolases, hydrases,oxido-reductases, desmolases, transferases and isomerases. All of theseenzymes may be used in the present invention. Particularly preferredenzymes are hydrolases such as proteases, esterases, carbohydrolases andnucleases.

Examples of proteases are pepsin, trypsin, chymotrypsin, collagenase,keratinase, elastase, subtilisin, BPN, papain, bromelin,carboxypeptidases A and B, aminopeptidase and aspergillopeptidases A andB.

Examples of esterases are gastric lipase, pancreatic lipase, vegetablelipases, phospholipases, cholinesterases and phosphotases.

Carbohydrolases include alkali cellulases, maltase, saccharase, amylase,pectinase, lysozyme, α-glycosidase and β-glucosidase.

[6] BLUING AGENTS AND FLUORESCENT DYES

Various bluing agents and fluorescent dyes may be incorporated in thecomposition, if necessary. For example, compounds of the followingstructures are recommended: ##STR33## and bluing agents of the generalformulae: ##STR34## wherein D represents a residue of blue or purple,monoazo, disazo or anthraquinone dye, X and Y each represent hydroxylgroup, amino group, an aliphatic amino group which may be substitutedwith hydroxyl, sulfonic acid, carboxylic acid or alkoxyl group, or anaromatic or alicyclic amino group which may be substituted with ahalogen atom or hydroxyl, sulfonic acid, carboxylic acid, lower alkyl orlower alkoxyl group, R represents a hydrogen atom or a lower alkyl groupbut excluding cases wherein (1) R represents a hydrogen atom and both Xand Y represent a hydroxyl group or an alkanolamine at the same time and(2) R represents a hydrogen atom, one of X and Y represents a hydroxylgroup and the other represents an alkanolamine group, and n representsan integer of at least 2, and ##STR35## wherein D represents a residueof a blue or purple, azo or anthraquinone dye, and X and Y may be thesame or different and represent an alkanolamine residue or a hydroxylgroup.

[7] CAKING-PREVENTING AGENTS

The following caking-preventing agents may be incorporated in powderydetergent composition: p-toluenesulfonate salts, xylenesulfonate salts,acetate salts, sulfosuccinate salts, talc, finely pulverized silica,clay, calcium silicates (such as Micro-Cell of Johns-Manvill Co.),calcium carbonate and magnesium oxide.

[8] ANTIOXIDANTS

The antioxidants include, for example, tert-butylhydroxytoluene,4,4'-butylidenebis(6-tert-butyl-3-methylphenol),2,2'-butylidenebis(6-tert-butyl-4-methylphenol), monostyrenated cresol,distyrenated cresol, monostyrenated phenol, distyrenated phenol and1,1'-bis(4-hydroxyphenyl)cyclohexane.

[9] STABILIZER FOR THE PEROXIDE AND AN ADDUCT TO HYDROGEN PEROXIDE

A stabilizer may be used in the bleaching detergent composition,including a magnesium salt such as magnesium sulfate, magnesiumsilicate, magnesium chloride, magnesium silicofluoride, magnesium oxideand magnesium hydroxide and a silicate such as sodium silicate.

EXAMPLES

The following examples will further illustrate the present invention,which by no means limit the invention.

Example 1

Preparation of ##STR36##

62.8 g of dimethyloctylamine was dissolved in 300 ml of ethanol in a 1-ltwo-necked flask provided with a condenser tube. 78.0 g of ethylbromobutyrate was added dropwise to the solution. After the completionof the addition, the temperature was elevated in an oil bath (90° C.)and the reaction was continued until the starting amine became no moredetectable under reflux of ethanol under examination according to TLC.Thus, ethanol was distilled off to obtain 140.5 g of a quaternary saltof the following formula (II-a): ##STR37##

yield: 99.8%.

40.8 g of the compound (II-a) was dissolved in 4 l of a solvent mixtureof ethanol/water (1:3) and hydrolysis was conducted at room temperaturefor 3 or 4 days while the pH was kept at 12 to 12.5 with KOH. Afterconfirming that the starting quaternary salt had been spent according toTLC, the reaction mixture was neutralized with 20% sulfuric acid and thesolvent was distilled off while a salt formed was filtered off. Aremaining oily substance was desalted with dichloromethane to obtain28.0 g of an amphoteric surfactant of the following formula (III-a):##STR38##

yield: 99.4%.

46.5 g of the compound (III-a) was dissolved in 250 ml ofdichloromethane in a 500-ml two-necked flask. 20 ml of thionyl chloridewas added dropwise to the solution at room temperature and the reactionwas conducted under reflux for 1 h. The solvent and excess thionylchloride were distilled off to obtain 57.0 g of a compound of thefollowing formula (IV-a) as an orange oily substance: ##STR39##

yield: 100%.

50.0 g of the acyl chloride (IV-a) was dissolved in 400 ml ofdimethoxyethane (DME) which had been dehydrated with lithium aluminumhydride and distilled. Disodium p-phenolsulfonate prepared by a processwhich will be described hereinbelow was added to the solution and thesuspension thus obtained was reacted under reflux for 2 h. DME wasremoved by decantation. Acetone was added thereto and the mixture wasstirred at room temperature. An acetone-soluble matter was removed byfiltration to obtain a mixture of sodium chloride with the compound(I-a). By recrystallization from ethanol/acetone, 26.8 g of white platycrystals were obtained.

yield: 40.0%.

m.p. 217°˜227° C.

IR (KBr, cm⁻¹): 2932, 2860, 1758, 1491, 1197, 1152, 1122, 1029, 1011,687, 567

¹ H-NMR (CD₃ OD solvent, TMS internal standard, δ): 1.0 (3H, t), 1.3˜1.5(12H, m), 2.1˜2.2 (2H, m), 2.7 (2H, t), 3.05 (6H, s), 3.35˜3.45 (2H, m),7.2 (2H, d), 7.85 (2H, d)

Preparation of disodium p-phenolsulfonate

278.4 g of sodium p-phenolsulfonate dihydrate was dissolved in 200 ml ofwater. 52 g of sodium hydroxide was added to the solution and themixture was stirred at room temperature for 2 h. Disodiump-phenolsulfonate thus crystallized out was separated by filtration. Thefiltrate was further subjected to the recrystallization. The crystalswere dehydrated with a Dean-Stark reflux condenser using toluene as thesolvent and then refluxed through a molecular sieve to thoroughlydehydrate them. 228 g of disodium p-phenolsulfonate was obtained.

yield: 87.4%.

Example 2

Preparation of ##STR40##

The compound (I-b) was prepared in the same manner as that of Example 1except that dimethyloctylamine was replaced with dimethyldodecylamine.

The yield obtained after the 4-stage reaction was 53.8%.

m.p. 213°˜216° C.

IR (KBr, cm⁻¹): 2920, 2854, 1755, 1497, 1470, 1221, 1191, 1122, 1032,1011, 693, 567

¹ H-NMR (CD₃ OD, TMS internal standard, δ): 0.9 (3H, t), 1.2˜1.45 (20H,m), 1.7˜1.9 (2H, m), 2.05˜2.2 (2H, m), 2.73 (2H, t), 3.09 (6H, s),3.3˜3.45 (2H, m), 7.15 (2H, d), 8.87 (2H, d)

Example 3

Preparation of ##STR41##

52 g of ethyl bromoacetate was dissolved in 250 ml of acetone in a1,000-ml three-necked flask. Dry gaseous trimethylamine carried by N₂gas was bubbled through the solution under stirring with a magneticstirrer. After two equivalents of trimethylamine per equivalent of ethylbromoacetate was bubbled over a period of 3 h, the flask was closed andthe mixture was stirred at room temperature overnight. White crystalsthus formed were separated by filtration to obtain 57.9 g of a compoundof the following formula (II-c): ##STR42##

yield: 85.4%.

50.65 g of the compound (II-c) was dissolved in 1 l of a solvent mixtureof ethanol/water (1:1) and hydrolysis was conducted at room temperaturefor 3 or 4 days while the pH was kept at 12 to 12.5 with KOH. Afterconfirming that the starting quaternary salt had been spent according toTLC, the reaction mixture was neutralized with 20% sulfuric acid and thesolvent was distilled off while a salt formed was filtered off. Aremaining oily substance was desalted with methanol to obtain 32.7 g ofan amphoteric compound of the following formula (III-c): ##STR43##

yield: 99.0%.

Thereafter, the same procedure as that of Example 1 was repeated toobtain the compound of the formula (I-c). The yield obtained after the4-stage reaction was 42.5%.

IR (KBr, cm⁻¹): 3034, 1749, 1593, 1494, 1194, 1071, 1029, 1011, 699, 567

¹ H-NMR (D₂ O, DSS internal standard, δ): 0.9˜2.5 (4H, m), 2.7 (2H, t),3.1 (9H, t), 7.2 (2H, d), 7.9 (2H, d)

EXAMPLE 4

Synthesis of ##STR44##

In a three-necked flask having a capacity of 1000 ml, 52 g of ethylbromobutyrate was dissolved in 250 cc of acetone, and the solution wasbubbled by dry trimethylamine by using gaseous N₂ as a carrier gas understirring with a magnetic stirrer. Trimethylamine was passed through thesolution in an amount of 2 equivalents to ethyl bromobutyrate over aperiod of 3 hours. Then, the flask was sealed and the reaction liquidwas stirred at room temperature overnight.

The formed white crystal was recovered by filtration to obtain 57.9 g of(II-d) in a yield of 85.4%: ##STR45##

Then, 50.65 g of (II-d) was dissolved in 1 l of a mixed solvent ofethanol/water (1/1) and hydrolysis was conducted at room temperature for3 to 4 days while maintaining the pH value at 12 to 12.5 with KOH. Afterconsumption of the starting quaternary salt was confirmed by TLC, thereaction liquid was neutralized with 20% sulfuric acid, and the solventwas removed by distillation while performing the filtering operationwhen a salt was formed. The salt was removed from the remaining oilysubstance by using methanol to obtain 32.7 g of a substance of thefollowing formula (III-d) in a yield of 99.0%: ##STR46##

In a two-necked flask having a capacity of 2000 ml, 220.3 g of (III-d)was dissolved in 300 g of chloroform, and 361.6 g of thionyl chloridewas dropped to the solution at room temperature. A reaction was carriedout under reflux for 1 hour. Removal of the solvent and excessivethionyl chloride by distillation gave 369.4 g of (IV-d) in the form ofan orange oily substance.

(the yield was 121.6%): ##STR47##

In a three-necked flask having a capacity of 5000 ml, 209.7 g ofp-hydroxybenzoic acid was dissolved in 2100 g of THF and 477.1 g ofdimethyloctylamine was added to the solution. 369.4 g of the acidchloride obtained above was added dropwise to the solution at roomtemperature with stirring. After termination of the dropwise addition,the reaction liquid was stirred at room temperature for 1 hour andfiltered, and the obtained crystal was washed with acetone and aceticacid to obtain 22.8 g of a crude hydrochloride of (I-d) in a yield of48.2%: ##STR48##

Physical Properties of (I-d)

Melting point: 250° to 253° C.

IR (KBr, cm⁻¹): 3010, 2830, 2570, 1758, 1704, 1611, 1419, 1383, 1227,1167, 1116, 1098, 909, 867

¹ H-NMR (CD₃ OD solvent, TMS internal standard δ): 1.95-2.5 (2H, m), 2.8(2H, t), 3.2 (9H, s), 3.5 (2H, t), 7.25 (2H, d), 8.1 (2H, d)

EXAMPLE 5

Synthesis of ##STR49##

In a three-necked flask having a capacity of 5000 ml, 194.4 g ofsalicylic acid was dissolved in 1500 g of THF and 442.4 g ofdimethyloctylamine was added to the solution. 339.1 g of the acidchloride (IV-d) obtained according to the process of Example 4 was addeddropwise to the solution at room temperature. After termination of thedropwise addition, the reaction liquid was stirred at room temperaturefor 1 hour and filtered. The obtained crystal was washed with acetone toobtain 269.1 g of a hydrochloride of the formula (I-e) in a yield of63.3%): ##STR50##

Physical Properties of (I-e)

Melting point: 167° to 171° C.

IR (KBr, cm⁻¹): 3016, 2740, 2578, 1764, 1710, 1611, 1491, 1455, 1416,1389, 1272, 1245, 1203, 1155, 1119, 1083, 792, 747

¹ H-NMR (CD₃ OD, TMS internal standard δ) 1.8-2.5 (2H, m), 2.75 (2H, t),3.2 (9H, s) 3.5 (2H, t), 7.1-8.2 (4H, m)

EXAMPLE 6

The obtained compounds (I-a), (I-b), (I-d) and (I-e) were examined inthe test on the bleaching action. Results of evaluation of the bleachingeffect according to the method described below are shown in Table 1.

Bleaching Method

Hydrogen peroxide was added to 300 ml of water at 20° C. so that theeffective oxygen concentration was 0.05% and 1 g of sodium carbonate wasadded. The compounds (I-a), (I-b), (I-d) and (I-e) were added to therespective solutions in an equimolar amount to hydrogen peroxide. Ablack tea-stained fabric prepared according to the method describedbelow was immersed in the solution for 30 minutes. The fabric was washedwith water and dried, and the bleaching ratio was calculated accordingto the formula described below. Sodium hypochlorite as a comparativesample was evaluated at an effective chlorine concentration of 0.06%.

Bleaching Ratio of Black Tea-stained Fabric: ##EQU1##

The reflectance was measured by using NDR-101DP supplied by NipponDenshoku Kogyo K. K. and a 460 nm filter.

Black Tea-stained Fabric:

                                      TABLE 1                                     __________________________________________________________________________                 Present                                                                       invention       Comparative                                                   1   2   3   4   5   6                                            __________________________________________________________________________    Component and                                                                         H.sub.2 O.sub.2                                                                    0.106                                                                             0.106                                                                             0.106                                                                             0.106                                                                             0.106                                                                             --                                           its conc. in                                                                          I-a  1.25                                                                              --      --  --  --                                           solution (%)                                                                          I-b  --  1.42                                                                              --  --  --  --                                                   I-d  --  --  1.02                                                                              --  --  --                                                   I-e  --  --  --  1.02                                                                              --  --                                                   NaOCl                                                                              --  --  --  --  --  0.063                                                Na.sub.2 CO.sub.3                                                                  0.333                                                                             0.333                                                                             0.333                                                                             0.333                                                                             0.333                                                                             --                                                   NaOH --  --  --  --  --  0.01                                         Available oxygen                                                                           0.05                                                                              0.05                                                                              0.05                                                                              0.05                                                                              0.05                                                                              --                                           concentration (%)                                                             Available chlorine                                                                         --  --  --  --  --  0.06                                         concentration (%)                                                             Bleaching ratio (%)                                                                        78  70  75  74  21  63                                           __________________________________________________________________________

In 3 l of deionized water, 80 g of black tea (Yellow Package supplied byNitto Kocha) was boiled for about 15 minutes, and the liquid wasfiltered through a paste-free bleached cotton cloth, and a cotton fabricof shirting #2003 was immersed in the liquid and boiled for about 15minutes. The fabric was taken out, allowed to stand still for about 2hours and spontaneously dried. Then, the fabric was washed with wateruntil the washing became colorless. The fabric was dehydrated, pressedand cut into a size of 10 cm×10 cm, and the obtained test piece wassubjected to the test.

EXAMPLE 7

A bleaching composition as shown in Table 2 was prepared from eachactivator obtained in Examples 1 and 2.

The bleaching effect of the composition was examined to obtain theresults shown in Tables 2 and 3.

Bleaching Effects Obtained by Immersion Bleaching method (Table 2)

Sodium percarbonate was dissolved in 300 ml of water at 20° C. to obtaina solution having an available oxygen concentration of 0.05%. Theactivator was added to the solution in an amount equimolar to hydrogenperoxide. Five sheets (8 cm×8 cm) of a cloth stained with black teaprepared as will be described below were immersed therein for 30 min,washed with water and dried. The bleaching rate was determined accordingto the following equation. The available oxygen concentration ofcomparative magnesium monoperphthalate hexahydrate was 0.05% andavailable chlorine concentration of comparative sodium hypochlorite was0.06%.

Bleaching rate of cloth stained with black tea: ##EQU2##

The reflectivity was determined with NDR-101DP (a product of NipponDenshoku Denko Co., Ltd.) using a 460 nm filter.

Cloth stained with black tea:

80 g of black tea leaves (yellow packages of Nitto Black Tea) wereboiled in 3 l of ion-exchanged water for about 15 min and then filteredthrough a desized, bleached cotton cloth. A cotton shirting #2003 wasimmersed in the filtrate under boiling for about 15 min. The mixture wasleft to stand without heating for 2 h and then spontaneously dried. Thecloth was washed with water until the wash water was no more colored,then dehydrated and pressed. The cloth was cut into test pieces having asize of 8 cm×8 cm, which were examined in the tests.

                  TABLE 2                                                         ______________________________________                                                      Present                                                                       in-                                                                           vention                                                                             Comparative                                                             7.sup.(3)                                                                         8.sup.(3)                                                                           9.sup.(3)                                                                           10.sup.(3)                                                                         11.sup.(4)                                                                           12.sup.(3)                          ______________________________________                                        Component                                                                             Sodium      23    20  68  --   --     100                                     percarbonate                                                                  I-a         77    --  --  --   --     --                                      I-b         --    80  --  --   --     --                                      TAED.sup.(1)                                                                              --    --  32  --   --     --                                      Magnesium   --    --  --  85   --     --                                      mono-                                                                         perphthalate.sup.(2)                                                          NaOCl       --    --  --  --   6.3    --                                      Na.sub.2 CO.sub.3                                                                         --    --  --  15   --     --                                      NaOH        --    --  --  --   0.5    --                                      Water       --    --  --  --   balance                                                                              --                              Bleaching rate (%)                                                                            78    70    51  58   63      21                               ______________________________________                                         .sup.(1) tetraacetylethylenediamine (a product of Hoechst)                    .sup.(2) a product of INTEROX                                                 .sup.(3) solution having an available oxygen concentration of 0.05%           .sup.(4) solution having an available chlorine concentration of 0.06%    

Bleaching Effects of a Bleaching Composition Used in Combination With aDetergent (Table 3)

Five sheets (8 cm×8 cm) of the cloth stained with black tea prepared asdescribed above were washed with a wash solution containing 0.133% of acommercially available heavy duty detergent and the detergentcomposition 7, 8, 9, 10 or 12 shown in Table 2 in such an amount thatthe available oxygen concentration would be 0.0033% with a turgotometerat 20° C. for 10 min. They were then washed with water and dried. Thebleaching rates of them were determined by the above-mentioned method.In case of the comparative sample 11, the bleaching agent was added tothe detergent of the above-mentioned concentration in such an amountthat the available chlorine concentration would be 0.014% and thebleaching rate was determined in the same manner as that describedabove.

                  TABLE 3                                                         ______________________________________                                                    Present                                                                       invention                                                                            Comparative                                                ______________________________________                                        Bleaching composition                                                                       7.sup.(1)                                                                           8.sup.(1)                                                                            9.sup.(1)                                                                           10.sup.(1)                                                                         11.sup.(2)                                                                          12.sup.(1)                        Bleaching rate (%)                                                                          41    27     10    11   38    3                                 ______________________________________                                         .sup.(1) available oxygen concentration: 0.0033%                              .sup.(2) available chlorine concentration: 0.014%                        

EXAMPLE 8

The three bleaching compositions, containing no phosphorus, a smallamount of phosphorus and a considerable amount of phosphorus,respectively, were obtained in the below shown formulations. Percent isbased on weight.

The composition containing no phosphorus was obtained from 14% of sodiumlinear dodecylbenzene sulfonate, 6% of polyoxyethylene (10 moles of EO)C12 to C13 alkyl ether, 2% of sodium salt of hardened beef tallowaliphatic acid, 5% of sodium silicate of 2 go, 10% of sodium carbonate,25% of zeolite of the 4A type, 10% of sodium percarbonate, 10% of theamphoteric compound (I-a), 2% of polyethylene glycol having a molecularweight of 6,000, 2% of protease, 4% of water and the balance of sodiumsulfate.

The compound having a small amount of phosphorus was obtained from 10%of sodium linear dodecylbenzene sulfonate, 2% of sodium dodecylsulfate,8% of polyoxyethylene (7.7 moles of EO) C12 to C13 alkyl ether, 2% ofsodium salt of hardened beef tallow aliphatic acid, 5% of sodiumsilicate of 1 go, 10% of sodium carbonate, 20% of zeolite of the 4Atype, 15% of sodium pyrophosphate, 10% of sodium perborate, 5% of theamphoteric compound (I-e), 1% of polyethylene glycol having a molecularweight of 11,000, 1% of sodium sulfite, 2% of protease, 4% of water andthe balance of sodium sulfate.

The compound containing a considerable amount of phosphorus was obtainedfrom 20% of polyoxyethylene (8.6 moles of EO) beef tallow alcohol ether,2% of sodium salt of hardened beef tallow aliphatic acid, 30% of sodiumtripolyphosphate, 10% of sodium perborate, 5% of the amphoteric compound(I-c), 5% of sodium silicate of 2 go, 10% of sodium carbonate, 1% ofsodium sulfite, 2% of polyethylene glycol having a molecular weight of6,000, 2% of protease, 6% of water and the balance of sodium sulfate.

What is claimed is:
 1. A bleaching composition, comprising:a peroxidebleaching agent, and an amphoteric organic per acid precursor or itssalt having the formula ##STR51## wherein R₁ and R₂ each represents asubstituted or unsubstituted, straight chain or branched alkyl oralkenyl having 1 to 30 carbon atoms, alkaryl in which the alkyl has 1 to24 carbon atoms, or ##STR52## forms a heterocyclic ring having 4 to 6carbon atoms; R₃ represents a substituted or unsubstituted,straight-chain or branched alkyl or alkenyl group having 1 to 30 carbonatoms, alkaryl in which the alkyl group has 1 to 16 carbon atoms, --(C₂H₄ O)_(x) H in which x is a number of from 1 to 20 or ##STR53## forms aheterocyclic ring having 4 to 6 carbon atoms; Y represents astraight-chain or branch alkylene having 1 to 20 carbon atoms, and Zrepresents SO₃ ⁻, CO₂ ⁻, or a hydrohalide thereof.
 2. A composition asclaimed in claim 1 in which said peroxide bleaching agent is hydrogenperoxide or a peroxide effective to release hydrogen peroxide in anaqueous solution.
 3. A bleaching detergent composition comprising ableaching composition as claimed in claim 1 in combination with awater-soluble, synthetic, organic surface active material.
 4. Acomposition as claimed in claim 1 in which the molar ratio of saidperoxide bleaching agent/said amphoteric organic per acid precursor isfrom 99.9/0.1 to 20/80.
 5. A composition as claimed in claim 1 in whichsaid peroxide bleaching agent is selected from the group consisting ofsodium carbonate/hydrogen peroxide adduct, sodiumtripolyphosphate/hydrogen peroxide adduct, 4Na₂ SO₄.2H₂ O₂.NaCl, sodiumpyrophosphate/hydrogen peroxide adduct, urea/hydrogen peroxide adduct,sodium perborate monohydrate, sodium perborate tetrahydrate, sodiumperoxide and calcium peroxide.
 6. A composition as claimed in claim 1 inwhich said amphoteric organic acid precursor has the formula ##STR54##7. A composition as claimed in claim 1 in which said amphoteric organicacid precursor has the formula ##STR55##
 8. A bleaching composition,comprising:a peroxide bleaching agent, and an amphoteric organic peracid precursor having the formula ##STR56## wherein R₁ is alkyl orhydroxyalkyl having 1 to 22 carbon atoms; R₂ and R₃ each representsalkyl having 1 to 3 carbon atoms; Y is alkylene having 1 to 5 carbonatoms; and Z represents SO₃ ⁻, CO₂ ⁻, or a hydrohalide thereof.
 9. Acomposition as claimed in claim 8 in which said peroxide bleaching agentis hydrogen peroxide or a peroxide effective to release hydrogenperoxide in an aqueous solution.
 10. A bleaching detergent compositioncomprising a bleaching composition as claimed in claim 8 in combinationwith a water-soluble, synthetic, organic surface active material.
 11. Acomposition as claimed in claim 8 in which the molar ratio of saidperoxide bleaching agent/said amphoteric organic per acid precursor isfrom 99.9/0.1 to 20/80.
 12. A composition as claimed in claim 8 in whichsaid peroxide bleaching agent is selected from the group consisting ofsodium carbonate/hydrogen peroxide adduct, sodiumtripolyphosphate/hydrogen peroxide adduct, 4Na₂ SO₄.2H₂ O₂.NaCl, sodiumpyrophosphate/hydrogen peroxide adduct, urea/hydrogen peroxide adduct,sodium perborate monohydrate, sodium perborate tetrahydrate, sodiumperoxide and calcium peroxide.
 13. A composition as claimed in claim 8in which said amphoteric organic acid precursor has the formula##STR57##
 14. A composition as claimed in claim 8 in which saidamphoteric organic acid precursor has the formula ##STR58##